Green azo dyestuffs and process of making same



Patented Dec. 10, 1935 UNlTED STATES PATENT OFFICE GREEN AZO DYESTUFFS AND PROCESS OF MAKING SAME No Drawing. Application November 25,- 1932, Serial No. 644,277. In Great Britain March 19,

10 Claims.

This invention relates to the manufacture of dyed articles and it comprises processes of making such articles wherein the material to be dyed is impregnated with a diacylacetyldiamino compound and the impregnated material is treated with a diazotized aminoaryleneaminoanthraquinone compound; and it further comprises dyed materials having green shades obtained by the formation of the dye in situ; all as more fully hereinafter set forth and as claimed.

This case is a continuation in part of application No. 536,665, filed May 11, 1931.

It is known that yellow, orange and brown water-insoluble azo dyes and dyeings on vegetable fibers may be obtained by combining, in substance or on the fiber, a diazotized amine and an diacylacetyldiamino compound (compare Patent No. 1,505,569), but hues other than those ranging from yellow to brown, have not heretofore been produced.

I have now discovered means by which such other hues or shades, particularly green shades, may be obtained.

By my present process I can produce green dyeings on textiles by the so-called ice-color process; the dyeings being of satisfactory fastness. Also I may produce a green water-insoluble dyestufi in substance.

In my process, I obtain these green water insoluble dyes by reacting a diacylacetyldiamino compound with a diazotized aminoaryleneaminoanthraquinone compound. The diacylacetyldiamino compound may be represented by the probable formula:

C C C II II II 0 0 O and Also the linkage represented by X may be a direct linkage between the arylene nuclei giving the structure represented above as -RR-.

I have found that compounds containing this direct linkage between the arylene nuclei, are advantageous both in my process and in the products produced. For instance, compounds repre- 5 sented by the following formula:

H: H H H:

wherein R represents a para-phenylene nucleus and R3 represents an alkyl or benzene nucleus, are advantageous.

The aminoaryleneaminoanthraquinone compounds may be represented by the following formula:

N Rll 0 l wherein R11 represents an alkyl group and R4 represents hydrogen, chlorine, an alkyl or alkoxy group, are advantageous.

The new azo dyestuffs obtained by my processes may be represented by the following generic formula:

wherein the various symbols have the same significance, as heretofore generically set forth. Within this generic class there are many subgeneric classes, a few of which are represented by the following structural formulae:

have very good light fastness and are fast also to perspiration and rubbing. r

In order better to disclose the invention I give several specific embodiments thereof below. It i t P e t qq hat example/em P 1 7 until there is4 parts of diazonium compound in ly illustrativeand that the invention is in no way limited thereto.

Example 1 Cotton yarn is impregnated by Working for 30 minutes at 30 C. in a solution containing 3 grams per litre of diaceto-acetyl-o-tolidide with the addition of 14 grams per litre of common salt, squeezed and passed into a diazo solution obtained as described below, diluted with water 10 1000 parts of solution. The yarn is immediately dyed green. The dyed yarn is rinsed and finally soaped for hour at the boil in a bath containing 3 grams soap and'2 grams soda ash per litre. A bright green'shade of great fastness to washing, kier-boiling, etc., is produced. 1 The diazo solution is obtained by dissolving 34.3 parts of l-methylamino-4-p-aminoanilinoanthra uinone:

in 200 parts of sulfuric acid of 96 per cent strength, adding 600 parts of ice and 6.9 parts of sodium nitrite dissolved in 50 parts of water. When all the nitrite is introduced, water is added until all the diazonium salt is dissolved, a deep green solution being obtained. The parts above are by weight.

7 Example 2 A diazonium solution is prepared in the man- 40 ner described in the preceding example and is filtered. if necessary. It is run into a solution of 20 parts of diacetoacetyl-o-tolidide in 1000 parts of water containing 8 parts of sodium hydroxide, all'the parts being by weight. The mixture is stirred overnight, then heated to C. and the precipitated insoluble dyestufi filtered and well washed with cold water. When dry it forms a dark green or black powder dissolving in concentrated sulfuric acid' to give a bright green solution, which on addition of water becomes olive green and gives an olive green precipitate. The dyestuff is sparingly soluble in benzene to a clear green solution. The dyestufi gives a green lake pigment when mixed with or prepared in presence of the usual substrata.

Example 3 i ion- 65 7 (obtained according to the method referred to 7 below by use of 2-chloro-p-phenylenediamine instead of p-phenylenediamine) A similar bright green shade is produced and the washing and other fastness properties are alike excellent.

Similar dyeings are obtained when there are used as parents of the diazonium compound the compounds represented by the following formulae:

r r N-CH: N-CHI O O H II C C ir a O 0 l r H l H these compounds being producible by the method described in British specification No. 315,905.

Other compounds, for instance, those represented by the formulae:

may also be used.

Likewise there may be used also as coupling components instead of diacetoacetyl-o-tolidide, diacetoacetyl-4,4-diamino-benzophenone, diacetoacetyl- 4,4 '-diaminodipheny1urea, diaceto-acetylbenzidine, diacetoacetyldianisidine, diacetoacetyl-4,4-diaminostilbene, diacetoacetyl 4,4 diaminodiphenylmethane, dibenzoylacetyl-o-tolidide and the like.

That the dyeings obtained in accordance with the invention exhibit outstanding fastness to kier-boiling is shown when the test described by Rowe (of. Journal of the Society of Dyers and Colourists, 1931, (February) page 33) is applied. The test is as follows:

One 5 gram skein of dyed cotton was plaited with one 5 gram skein of bleached cotton yarn and boiled for six hours in 100 cc. distilled water to which 0.8 cc. 73 Tw. caustic soda solution had been added (i. e. 100 cc. of 0.36 per cent caustic soda solution). Loss of water by evaporation is continually made up by dropping in boiling water. The plait is removed, rinsed thoroughly in running water, and dried.

The fiber may also .be dyed in the novel way by printing a diazo solution upon a padded fabric in the usual manner.

As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. A process for producing azo dyes which comji Ha prises coupling a diazotized amino-aryleneamino-anthraquinone compound with a diacylacetyl-diamino compound wherein the acylacetyl groups are substituted on separate amino groups.

2. A process for producing azo dyes which comprises coupling a diacyl-diamino compound of the following general formula:

wherein R represents a diphenyl radical, with a diazotized amino-phenylene-amino-anthraquinone compound.

3. The process of claim 2 wherein the aminophenylene-amino-anthraquinone compound is a l-methylamino-para-amino phenylene aminoanthraquinone compound.

4. A process for producing azo dyes which comprises coupling a diacyldiamino compound of the following general formula:

wherein R represents a phenyl radical or a diphenyl radical which may have substituted thereon an alkyl group, with a diazotlzed aminophenyleneaminoanthraqulnone of the following formula:

O IIIHCHI 5. A process of producing green azo-dyestuffs 6. An azo dye having the: following general formula? wherein R represents the radical of a diazotized amino-arylene-amino-anthraquinone compound, and X represents the residue of a.diacyl-acetyldiamino compound wherein the acyl acetyl groups are substituted on separate amino groups.

7. An azo dye having the following general formula:

V t i N 'N wherein R represents a diphenyl radical and R represents the residue of a diazotized aminophenylene-amino-anthraquinone compound.

V in which Rrepresentsa para-phenylene nucleus.

QLAnazo dye having the following general formula;

' (if NHCH O NHCH:

It cHr-c 0-(33-0 O-NH-R-NH-C o-r'm-oo-om wherein R represents a phenyl radical or a di- 20 phenyl radical which may have substituted thereon an alkyl group.

10. The azo-dyestufi of the formula:

I C Hr-NH V formula:

6 'NHCH:

8. An azo dye having the following general being insoluble in water and yielding, when produced on the fiber, green dyeings of good fast- 40 H r r H ness properties. a 7 WILLIAM GALLOWAY REID. o on, (H \CH| c l 0 ll 3 v III-11 V i i-H if i if 

